Azo dyestuffs and their production



Patented June 2, 1936 PATENT [om-ice v AZO nms'rms'ann 'rnnra monUc'rroN Wilhelm Koch and Herman Winkeler, Ludwig!- haien-on-the-Bhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application December 18. 1934,

Serial No. 758,142. In Germany October 31,

7 Claims.

The present invention relates to new azo dyestuffs and a process of producing same.

We have found that azo dyestuffs which are capable of being chromed in substance or on the fibre and which have very good properties as regards iastness are obtained by diazotizing compounds, corresponding to the general formula in which X stands for a radicle of the benzene and naphthalene series, the amino and hydroxyl group standing in ortho-position to each other, and in which X is further substituted by at least one negative substituent, selected from the group consisting of the nitro group and halogen atoms and coupling the said compounds with compounds having the general formula:

Y Y Y Y I on O OH in which R1 and R2 stand for organic radicles selected from the group consisting of aliphatic, and aromatic radicles or for members of a cycloaliphatic ring, and Y stands for hydrogen or a substituent. Suitable diazo components are for example diazo compounds of l-hydroxy-Z amino-4-nitrobenzene-6-sulphonic acid, l-hydroxy-2-amino-4-chlorbenzene-6-sulphonic acid, 1-hydroxy-2-amino-4 -nitro- 6 -chlorbenzene, 1 hydroxy-2-amino-4, 6 -dinitrobenzene. Suitable coupling components are for example condensation products derived from 1 molecular proportion of a ketone and 2 molecular proportions of a phenol or its derivatives, as follows: beta-betadi-(4-hydroxy phenyl) -propane, beta-beta-di- (4-hydroxyphenyl) butane, beta-beta-di- (i-hydroxy 3 sulphophenyi) -propane, beta-beta-di- (4 hydroxy 3 methylphenyl) propane, betabeta-(4-hydroxyphenyl)'-cyclohexane, beta-betadi-(4 hydroxyphenyl) beta-phenyl-ethane. In the said manner monoazo dyestuffs and in some cases disazo dyestuffs may be prepared which in the form of their chromium compounds or by after-chroming on the fibre yield dyeings which are very fast to fulling and washing.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are y ght. r

Example 1 The solution of the diazo compound of 234 parts of 1 -hydroxy-2-amino-i-nitrobenzene 6 sulphonic acid, prepared in the usual manner, is allowed to flow into a solution of 250 parts of beta-beta-di-(4 -hydroxyphenyl) -propane in a mixture of 5000 parts of water, 100 parts of canstic soda of 40 B. strength and 200 parts of sodium carbonate, the whole being stirred until the coupling is completed. The resulting dyestuif is then salted out by the addition of common salt.

The dyeing produced with the dyestufl on wool is subjected to after-chroming whereby brown shades of excellent fastness to light, washing and iulling are obtained. The chromium compound of the dyestuff when prepared in substance dyes wool reddish brown shades of similar excellent fastness.

Example 2 Example 3 The diazo -compound obtained from 188, 5 parts of 1-hydroxy-2-amino-4-nitro-6-chlorbenacne is coupled in the usual manner with 420 parts of betabeta-d1 (4 hydroxy 3 sulphuphen'yl) -propane in a solution rendered alkaline with sodium carbonate. When the coupling is completed the dyestuff is salted out by the addition of common salt. It dyes wool very uniform brown shades which change to a brown fast to washing, iulling and light by after-treatment I with bichromate.

Example 4 The 'diazo compound obtained from 234 parts of l-hydroxy-Z-amino- 4 nitrobenzene 6 sulphonic acid is coupled in the usual manner with 290 parts of 1 -di-(4 -hydroxyphenyl) cyclohexane dissolved in a mixture of 10,000 parts of water, 200 parts of caustic soda solution of 40 Be.

. strength and 200 parts of sodium carbonate. The

dyestuif separated by salting out with common salt in the usual manner yields brown dyeings on wool which change to a brown of excellent fastness by after-chroming.

Example 5 The solution of the compound of 234 parts of l-hydroxy-2-amino-4-nitrobenzene -6- sulphonic acid, prepared in the usual manner, is allowed to flow into an ice-cooled solution of 280 parts of beta-beta-di- (4-hydroxy-3-methylphenyl) propane in 5000 parts of water, 150 parts 01! sodium hydroxide of 40 B. and 200 parts of sodium carbonate, the whole being stirred until the coupling is completed. The dyestufi separated by salting out with common saltyields on wool by afterchroming brown shades of good'fastness.

Example 6 The diazo compound obtained from 234 parts of l-hydroxy-2-amino-4-nitrobenzene -6- sulphonic acid is coupled in the usual manner with 260 parts of beta-beta-di-(4-hydroxyphenyl) -butane in a solution rendered alkaline with sodium carbonate. The resulting dyestufi dyes wool by after chroming brown shades of excellent iastness.

Example 7 The solution of the diazo compound of 199 parts of 1-hydr'oxy-2-amino-4, fi-diniti'obenzene, prepared in the usual manner, is allowed to flow into a solution "of 250 parts 'of beta-beta-di-(4-hy-' dyestufi separated by salting out with common salt dyes woolby after chroming red brown shades of excellent fastness to washing, fulling and finishing.

What we claim is:-

1. The process of producing azo dyestufis capable of being chromed which comprises diazotizing a compound corresponding to the general formula:

in which X stands for a radicle of the benzene .and naphthalene series, the amino and hydroxyl group standing in ortho-position to each. other, and in which X is further substituted by at least one negative substituent selected from the group consisting'of the nitro group and halogen atoms, and coupling the said diazotized compound with a compound having the general formula:

0H c on Y Y. Y in which R1 and R: stand for organic radicles selected-from the group consisting of aliphatic and aromatic radicies or represents a cyclo-aliphatic ring, and one Y in each of the' benezene nuclei shown represents a member of the group consisting of hydrogen, a methyl and -SO3H group, the other Y's being hydrogen.

2. The process oi producing azo dyestufis capable of being chromed which comprises diazotizing a compoond corresponding to the general 10rmula:

BIN

in which X stands -ior a radicle oi the benzene and naphthalene series, the amino and hydroxyl group standing in ortho-posltion to each other, and in which X is further substituted by atleast one nitro group and at least one halogen atom, and coupling the said diazotized compound with a compound having the general formula:

YY Y'Y in which and-R: stand for organlc,radicles 5 selected from the group consisting of aliphatic and aromatic radicles o"r I f represents a cyclo-aliphatic ring, and one Y in each of the benzene nuclei shown represents a member of the group consisting of hydrogen, a

methyl and -S03H group, the other Ys being hydrogen.

3. The process of producing azo dyestufis capable of being chromed which comprise fllazotizing a compound corresponding to the general formula:

H1N\x 011 inwhichx stands for a radicle of the benzene and naphthalene series, the amino and hydroxyl group standing in ortho-position to each other,

and in which X is further substituted by at least one negative substituent selected from the group consisting of the nitro group and halogen atoms,

, and furthermore by at least one sulphonic' acid group, and coupling the said diazotized compound with a compound having the general formula:

- Y Y I Y Y Ri\\ /R| OH O OH in which R1 and R: stand for organic radicles selected from the group consisting of aliphatic and aromatic radlcles or' represents a cycle-aliphatic ring, and one Y in each of the benzene nuclei shown represents a member oi the group consisting of hydrogen, a methyl and -SO:H group, the other To being hydrogen.

d. The process of producing azo dyestufls capa-' ble of being chromed which comprises a compound corresponding to the general formula:

and coupling the said diasotized compound with a Y compound having the general formula;

Y Y Y r a 5* 0nQc on in which R1 and R: stand for organic radicles selected from the group of aliphatic I and aromatic radicles or B R, c

represents a cyclo-aliphatic ring and one Y in each or the benzene nuclei shown stands for the BOaH group, the other Y's being hydrogen.

5. Azo'dyestufls, capable of being chromed, of the general formula:

inwhichArepresentsaradicleotthediasoeomponent derived from a compound 7 to the general formula;

inwhlchxstamkfora'radicleotthebenseneand 304- eerewelentsaeselo-aliphatieringmd ym eachd-thebensmenucldshownmg. mmnberot mam.

, to the general formula:

, 3 u dyeatuils, capable oi being chromed. oi! the general formula:

' (4-1v=ua in which A represents a radicle oi the diano comcorresponding ponent derived from a compound HsN in which 2: stands for a radicle of the benzene and naphthalene series, the amino and hydroxyl group standing in ortho-position to each other, and in which x is further substituted by at .least one negative substituent selected from the group consisting of the nitro group and halogen atoms, B represents a radicle of the coupling component having the general formula:

in which R1 and Rs represent organic radicles at least one of which is an aliphatic radicle, and one Y in each oi. the benzene nuclei shown represents a member of the group consisting of hydrogen, a methyl and -BO:H group, the other Y's being hydrogen and n is 1 or 2.

'1. Aso dyestufls, capable oi being chromed. oi the general formula:

m which it represents a radicle or the diaso component derived from a compound corresponding to the general formula:

inwhichxstandstoraradicleottbebensenelnd naphthalene series,theaminoandhydroxylgroup standim in ortho-position to each other. and in which 1: is further substituted by atleast one negative substituent selected from the group conslstingotthenitrogrcupandhalogenatomaB represents aradicleottbeeouplinge havingtbegeneraltomuia:

Y- Y R n. Y Y I on v a inwhiehltrandnarepresentorganicradicleaat oneotwhichisanarcmaticradiclaandone eachotthebensenenueleishownrepresents manberotthegroupconsistingoihydrma and B0:H group. the other To being lmirogenandnisl-orz WILHIIMKOOH. 

